CN105316527B - A kind of nickel manganese gallium super-elastic shape memory alloy wire and preparation method thereof - Google Patents
A kind of nickel manganese gallium super-elastic shape memory alloy wire and preparation method thereof Download PDFInfo
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- CN105316527B CN105316527B CN201510835614.6A CN201510835614A CN105316527B CN 105316527 B CN105316527 B CN 105316527B CN 201510835614 A CN201510835614 A CN 201510835614A CN 105316527 B CN105316527 B CN 105316527B
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Abstract
The present invention relates to a kind of nickel manganese gallium super-elastic shape memory alloy wire and preparation method thereof, the molecular formula of the alloy is NixMnyGaz, wherein x+y+z=100, x=46~56, y=24~36, z=16~26.Its preparation method is to use glass fluxing technique spin processes, pass through high-frequency induction device, in the range of 300~800A, gradual melted alloy ingot, when bottom glass pipe softens, molten alloy liquid and bottom glass form a micro- molten bath, then glass tube bottom traction microfilament of the glass bar with tip from softening is used, the nickel manganese gallium super-elastic shape memory alloy microfilament of glass fluxing technique is obtained after water-spraying control, then the glass on surface is peeled off, obtains the naked silk of Ni Mn Ga super-elastic shape memory alloys.Process of the present invention is simple, and 3~200 μm of the microfilament diameter prepared, microfilament has excellent superelastic properties, is to integrate the intellectual material perceived with driving, can be widely applied in sensor and driver.
Description
Technical field
The present invention relates to nickel manganese gallium super-elastic shape memory alloy, belongs to sensor and intellectual material field.
Background technology
When marmem is in austenitic state, deform under stress, after stress removes, lured by stress
Deformation caused by hair martensitic traoformation disappears at once, and this effect is referred to as super-elasticity.With marmem application
Expand day by day, the requirement to material property and shape also increasingly improves.Develop the forms such as memorial alloy ultrafine wire, fiber
Functional material, minimizing, being intelligent for memory alloy element can be promoted.
Ni-Mn-Ga marmems are a kind of novel magnetic controlled marmems for starting the nineties in last century to occur,
By field drives martensitic twin variant reorientation, with up to 9.5% magneto-strain.In addition, by constituent adjustment,
Ni-Mn-Ga alloys can obtain up to 350 DEG C of martensite transformation temperature, thus it is also a kind of potential high temperature form note
Recall alloy material.
But Ni-Mn-Ga marmems only have ductility under monocrystalline state, polycrystalline is then due to coarse grains, generally
Fragility is presented.Monocrystalline silk material preparation difficulty is big, and efficiency is low, and cost is high.Polycrystalline alloy cold working is difficult, it is difficult to uses traditional cold-drawn
Technique prepares silk material, thus can not obtain practical application.
The content of the invention
For above-mentioned present situation, first technical problem to be solved by this invention is to provide a kind of nickel manganese gallium superelastic shape
Memory wire.Silk material crystal grain refinement is to micron order, with high 8% superelastic properties.
Second technical problem to be solved by this invention is to provide a kind of preparation method of nickel manganese gallium shape-memory wire, its
Preparation method is to use glass fluxing technique spin processes, by quickly cooling down, alloy is quickly solidified from fused solution, one-shot forming is
Silk material.
It is of the invention to be by the technical scheme that above-mentioned first technical problem is taken：Nickel manganese gallium super-elastic shape memory alloy
Silk, it is characterised in that the molecular formula of the alloy is NixMnyGaz, the atomic molar percentage of each corresponding alloying element of subscript expression,
Wherein x+y+z=100, x=46~56, y=24~36, z=16~26.
The present invention is a kind of nickel manganese gallium superelastic shape to solve the technical scheme that above-mentioned second technical problem is taken
The preparation method of memory alloy wire, comprises the following steps：
Step 1：By atomic molar percentage by Ni, Mn, Ga dispensing in component,
Ni 46~56%
Mn 24~36%
Ga 16~26%
With dilute HNO before dispensing3Cleaning Mn pieces are to remove its surface oxide layer, during preparation in view of Mn in fusion process
Volatilization, add 0.05% Mn.Wherein each material purity is all higher than 99%；
Step 2：The raw material prepared is being smelted into uniform foundry alloy under argon gas is protected under high-frequency electromagnetic induction effect,
Melting number is not less than 4 times, and the uniform foundry alloy of melting is crushed, is put into high-boron-silicon glass pipe；
Step 3：The glass tube for installing alloy material is vertically fixed, glass bottom of the tube is located at taper induction coil
In, glass tube openend links mechanical pump by bellows, is evacuated to below 5pa, then applying argon gas are to 0.1Mpa；
Step 4：Start high-frequency induction device, in the range of 300-800A, heated current is gradually stepped up, when alloy pig melts
Change, when bottom glass pipe softens, molten alloy liquid and bottom glass form a micro- molten bath, then use the sophisticated glass bar of band from
The glass tube bottom traction of softening goes out microfilament, and the alloy wire of glass fluxing technique is obtained after water-spraying control；
Step 5：The glass for preparing microfilament surface is peeled off, obtains Ni-Mn-Ga super-elastic shape memory alloy wires.
Crushed described in step 2 is the block that alloy pig is broken into 1~3g.
Temperature control during the micro- molten bath of formation described in step 4 is between 1000 DEG C~1300 DEG C.
The technical advantages of the present invention are that：
(1) memory wire can disposably be prepared using fluxing technique, process is simple, and preparation flow is short, without drawing and moves back
Fire, efficiency high, cost are low.
(2) fluxing technique cooldown rate is fast, crystal grain refinement to micron order, and silk material superelastic properties are excellent, and overall strain is
Unloaded when 10%, response rate reaches more than 99%, and superelastic strain has reached 8%.It is insoluble more to overcome traditional handicraft
Brilliant brittleness problems.
Brief description of the drawings
Fig. 1 is Ni in the embodiment of the present invention 154.89Mn23.52Ga21.60The ESEM of super-elastic shape memory alloy wire
(SEM) photo.
Fig. 2 is Ni in the embodiment of the present invention 154.89Mn23.52Ga21.60Unloaded after super-elastic shape memory alloy wire loading
Stress-strain curve.
Embodiment
Embodiment 1
The molecular formula of the nickel manganese gallium super elastic marmen silk of this example is Ni54.89Mn23.52Ga21.60, preparation process is such as
Under：Raw material Ni, Mn, the Ga of purity more than 99% are pressed into Ni53Mn26Ga21Into assignment system 20g, then with high-frequency induction smelting furnace
Melting is carried out under argon gas protection.Melted alloy pig is broken into 1~3g cobbing, by the conjunction that a fritter weight is 1.5g
Gold material is put into the bottom of high-boron-silicon glass pipe, glass tube external diameter 10mm, wall thickness 1mm.The glass tube for installing alloy material is fixed, opened
Mechanical pump is evacuated to 2.5Pa, then applying argon gas are to 0.1MPa.Start high-frequency induction device, gradually step up heated current to 600A,
Now alloy pig melts, and the softening of glass bottom of the tube, molten alloy liquid and bottom glass form a micro- molten bath.The temperature in micro- molten bath
Then control goes out the B alloy wire of glass fluxing technique with the glass bar with tip at 1200 DEG C or so from the glass tube bottom traction of softening
Material, the nickel manganese gallium super elastic marmen silk of glass fluxing technique is obtained after water-spraying control.The glass of the microfilament surface of preparation is shelled
Fall, obtain a diameter of 43.5 μm of the naked silk of nickel manganese gallium super-elastic shape memory alloy.Silk material ESEM (SEM) photo such as Fig. 1
It is shown.Due to the volatilization of manganese in fusion process, microfilament composition and raw material proportioning is caused to be deviated, the EDS analysis shows microfilament
Composition is Ni54.89Mn23.52Ga21.60.Loading and unloading test is carried out to microfilament using DMA, initial gage is~10mm, works as strain
For 10% when unload load, obtain loading-unloading stress-strain diagram as shown in Figure 2, curve shows to strain after unloading basic
Recover completely, microfilament has good superelastic properties.
Embodiment 2
The molecular formula of the nickel manganese gallium super elastic marmen silk of this example is Ni55.68Mn23.32Ga21, preparation process is as follows：
Raw material Ni, Mn, the Ga of purity more than 99% are pressed into Ni54Mn25Ga21Into assignment system 20g, then with high-frequency induction smelting furnace in argon
Melting is carried out under gas shielded.Melted alloy pig is broken into 1~3g small fast material, the alloy material that a fritter weight is 2g is put
Enter the bottom of glass tube.The glass tube for installing alloy material is fixed, start tool pump is evacuated to 2.5Pa, then applying argon gas are extremely
0.1MPa.Start high-frequency induction device, gradually step up heated current to 650A, now alloy pig fusing, glass bottom of the tube and soften,
Molten alloy liquid and bottom glass form a micro- molten bath.Then the temperature control in micro- molten bath uses band tip at 1250 DEG C or so
Glass bar go out the alloy wire of glass fluxing technique from the glass tube bottom traction of softening, glass fluxing technique is obtained after water-spraying control
Nickel manganese gallium super elastic marmen silk.The glass of the microfilament surface of preparation is peeled off, obtains a diameter of 55 μm of nickel manganese gallium superlastic
The property naked silk of marmem.The EDS analysis shows microfilament composition is Ni54.89Mn23.52Ga21.60。
Embodiment 3
The molecular formula of the nickel manganese gallium super elastic marmen silk of this example is Ni56.59Mn22.39Ga21.02, preparation process is such as
Under：Raw material Ni, Mn, the Ga of purity more than 99% are pressed into Ni55Mn24Ga21Into assignment system 20g, then with high-frequency induction smelting furnace
Melting is carried out under argon gas protection.Melted alloy pig is broken into 1~3g small fast material, by the conjunction that a fritter weight is 1.5g
Gold material is put into the bottom of glass tube.The glass tube for installing alloy material is fixed, start tool pump is evacuated to 2.5Pa, then applying argon gas
To 0.1MPa.Start high-frequency induction device, gradually step up heated current to 700A, now alloy pig fusing, glass bottom of the tube are soft
Change, molten alloy liquid and bottom glass form a micro- molten bath.Then the temperature control in micro- molten bath uses band point at 1300 DEG C or so
The glass bar at end goes out the alloy wire of glass fluxing technique from the glass tube bottom traction of softening, and glass fluxing technique is obtained after water-spraying control
Nickel manganese gallium super elastic marmen silk.The glass of the microfilament surface of preparation is peeled off, a diameter of 60 μm of nickel manganese gallium is obtained and surpasses
The naked silk of elastic shape memory alloy.The EDS analysis shows microfilament composition is Ni56.59Mn22.39Ga21.02。
In summary, a kind of nickel manganese gallium super-elastic shape memory alloy wire of the present invention and preparation method thereof is simple and easy.On
The technical concepts and features of embodiment only to illustrate the invention are stated, its object is to person skilled in the art can understand
Present disclosure is simultaneously carried out, and it is not intended to limit the scope of the present invention, all according to spirit of the invention institute
The equivalent change or modification of work, all cover within the scope of the present invention.
Claims (1)
1. a kind of preparation method of nickel manganese gallium super-elastic shape memory alloy wire, it is characterised in that comprise the following steps：
Step 1：By atomic molar percentage by Ni, Mn, Ga dispensing in component,
Ni 46~56%
Mn 24~36%
Ga 16~26%
With dilute HNO before dispensing3Cleaning Mn pieces are to remove its surface oxide layer, volatilization during preparation in view of Mn in fusion process,
Add 0.05% Mn, wherein each material purity is all higher than 99%；
Step 2：The raw material prepared is being smelted into uniform foundry alloy, melting under argon gas is protected under high-frequency electromagnetic induction effect
Number is not less than 4 times, within mass deviation 0.5g, the uniform foundry alloy of melting is crushed, is put into high-boron-silicon glass pipe；
Described crush is the block that alloy pig is broken into 1~3g；
Step 3：The glass tube for installing alloy material is vertically fixed, glass bottom of the tube is located in taper induction coil, glass
Glass tube opening end links mechanical pump by bellows, is evacuated to below 5pa, then applying argon gas are to 0.1MPa；
Step 4：Start high-frequency induction device, in the range of 300-800A, gradually step up heated current, when alloy pig fusing, bottom
During portion's glass tube softening, molten alloy liquid and bottom glass form a micro- molten bath, then use the glass bar with tip from softening
Glass tube bottom traction go out microfilament, the alloy wire of glass fluxing technique is obtained after water-spraying control；
Step 5：The glass for preparing microfilament surface is peeled off, obtains Ni-Mn-Ga super-elastic shape memory alloy wires；
Wherein, temperature control during the micro- molten bath of formation described in step 4 is between 1000 DEG C~1300 DEG C.
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| CN105908017A (en) * | 2016-04-20 | 2016-08-31 | 北京科技大学 | High-super-elasticity Ni-Fe-Ga-Co micro wire and preparation method of same |
| CN105950916B (en) * | 2016-05-25 | 2018-05-25 | 北京科技大学 | A kind of field drives torsion nickel cobalt manganese tin alloy silk and preparation method |
| CN105908051B (en) * | 2016-05-25 | 2018-01-02 | 北京科技大学 | A kind of preparation method of high super-elasticity NiMnSnCo alloy fine wires |
| CN110923510B (en) * | 2019-12-16 | 2021-08-31 | 大连大学 | Preparation method of high preferred orientation NiMnGa magnetic memory alloy wire |
| CN115369288B (en) * | 2022-08-14 | 2023-05-26 | 南昌航空大学 | Diphase Ni-Mn-Ga shape memory alloy and preparation method thereof |
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| CN1571083A (en) * | 2004-05-11 | 2005-01-26 | 钢铁研究总院 | A method for preparing Ni-Mn-Ga magnetic band |
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| CN104894428A (en) * | 2015-06-12 | 2015-09-09 | 北京科技大学 | Copper-based hyperelastic shape memory alloy wire and preparation method thereof |
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| CN1571083A (en) * | 2004-05-11 | 2005-01-26 | 钢铁研究总院 | A method for preparing Ni-Mn-Ga magnetic band |
| CN102127720A (en) * | 2011-01-30 | 2011-07-20 | 北京科技大学 | Method and device for continuously preparing superfine amorphous alloy wire |
| CN104152730A (en) * | 2014-09-05 | 2014-11-19 | 哈尔滨工业大学 | Preparation method for nickel-manganese-gallium alloy with superplasticity |
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